Microchimica Acta

, 186:95 | Cite as

Nanostructured MXene-based biomimetic enzymes for amperometric detection of superoxide anions from HepG2 cells

  • Jiushang Zheng
  • Bin WangEmail author
  • Yanzi Jin
  • Bo Weng
  • Jiucun ChenEmail author
Original Paper


A novel MXene-based biomimetic enzyme was synthesized using adenosine triphosphate (ATP) as a template to modify a Mn3(PO4)2 nanostructure on Mxene-Ti3C2 nanosheets. The resulting composite was used as an electrode material in an electrochemical sensor for superoxide anion (O2•−). It displays excellent catalytic properties which is attributed to the synergistic effects of the two-dimensional conductive substrate and the Mn3(PO4)2 nanoparticles. The addition of ATP results in the formation of a porous and ordered nanostructure of Mn3(PO4)2. This facilitates the electron transfer between O2•− and electrode. The sensor, best operated at 0.75 V (vs. Ag/AgCl), displays a rapid amperometric response with a detection limit of 0.5 nM and an analytical range that extends from 2.5 nM to 14 μM. Conceivably, it has potential in the detection of O2•− released by living cells.

Graphical abstract

Nanostructured MXenes were synthesized by in-situ growth of Mn3(PO4)2 on Ti3C2 nanosheets under the induction of adenosine triphosphate (ATP). They display enzyme mimickong properties. A sensor fabricated with the composites can be used for the detection of superoxide anions released by HepG2 cells.


Mxene-Ti2C3 Mn3(PO4)2 ATP Two-dimensional materials Sensor 



We gratefully acknowledge to the financial support by the China Postdoctoral Science Foundation (2016 M602627), National Natural Science Foundation of China (21505108), Chongqing Postdoctoral Science Special Foundation (Xm2016032), Transformative Project for Excellent Scientific and Technological Achievements in University (KJZH17108), Special Program for Chongqing Social Business and People’s Livelihood Guarantee of Science and Technology (cstc2017shmsA30001) and Science Foundation for Youths of Science and Technology Department of Shaanxi Province (2016JQ2026).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2018_3220_MOESM1_ESM.doc (2.9 mb)
ESM 1 (DOC 3003 kb)


  1. 1.
    Tang Q, Zhou Z, Shen P (2012) Are MXenes promising anode materials for Li ion batteries? Computational studies on electronic properties and Li storage capability of Ti3C2 and Ti3C2X2 (X = F, OH) monolayer. J Am Chem Soc 134:16909–16916CrossRefGoogle Scholar
  2. 2.
    Hu H, Bai Z, Niu B, Wu M, Hua T (2018) Binder-free bonding of modularized MXene thin films into thick film electrodes for on-chip micro-supercapacitors with enhanced areal performance metrics. J Mater Chem A 6:14876–14884CrossRefGoogle Scholar
  3. 3.
    Lorencova L, Bertok T, Dosekova E, Holazova A, Paprckova D, Vikartovska A, Sasinkova V, Filip J, Kasak P, Jerigova M, Velic D, Mahmoude KA, Tkac J (2017) Electrochemical performance of Ti3C2Tx MXene in aqueous media: towards ultrasensitive H2O2 sensing. Electrochim Acta 235:471–479CrossRefGoogle Scholar
  4. 4.
    Guo J, Peng Q, Fu H, Zou G, Zhang Q (2015) Heavy-metal adsorption behavior of two-dimensional alkalization-intercalated MXene by first-principles calculations. J Phys Chem C 119:20923–20930CrossRefGoogle Scholar
  5. 5.
    Naguib M, Kurtoglu M, Presser V, Lu J, Niu J, Heon M, Hultman L, Gogotsi Y, Barsoum MW (2011) Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Adv Mater 23:4248–4253CrossRefGoogle Scholar
  6. 6.
    Lukatskaya MR, Mashtalir O, Ren CE, Dall’Agnese Y, Rozier P, Taberna PL, Naguib M, Simon P, Barsoum MW, Gogotsi Y (2013) Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341:1502–1505CrossRefGoogle Scholar
  7. 7.
    Xu B, Zhu M, Zhang W, Zhen X, Pei Z, Xue Q, Zhi C, Shi P (2016) Ultrathin MXene-micropattern-based field-effect transistor for probing neural activity. Adv Mater 28:3333–3339CrossRefGoogle Scholar
  8. 8.
    Sinha A, Dhanjai, Zhao H, Huang Y, Lu X, Chen J, Jain R (2018) MXene: an emerging material for sensing and biosensing. Trends Anal Chem 105:424–435CrossRefGoogle Scholar
  9. 9.
    Wang F, Yang CH, Duan CY, Xiao D, Tang Y, Zhu JF (2015) TiO2 nanoparticle modified organ-like Ti3C2 MXene nanocomposite encapsulating hemoglobin for a mediator-free biosensor with excellent performances. Biosens Bioelectron 74:1022–1028CrossRefGoogle Scholar
  10. 10.
    Liu H, Duan C, Yang C, Shen W, Wang F, Zhu Z (2015) A novel nitrite biosensor based on the direct electrochemistry of hemoglobin immobilized on MXene-Ti3C2. Sensors Actuators B 218:60–66CrossRefGoogle Scholar
  11. 11.
    Rakhi RB, Nayak P, Xia C, Alshareef HN (2016) Novel amperometric glucose biosensor based on MXene nanocomposite. Sci Rep 6:36422–36431CrossRefGoogle Scholar
  12. 12.
    Zheng J, Wang B, Ding A, Weng B, Chen J (2018) Synthesis of MXene/DNA/Pd/Pt nanocomposite for sensitive detection of dopamine. J Electroanal Chem 816:189–194CrossRefGoogle Scholar
  13. 13.
    Zweier JL, Talukder MA (2006) The role of oxidants and free radicals in reperfusion injury. Talukder, Cardiovasc Res 70:181–190CrossRefGoogle Scholar
  14. 14.
    Ganesana M, Erlichman JS, Andreescu S (2012) Real-time monitoring of superoxide accumulation and antioxidant activity in a brain slice model using an electrochemical cytochrome c biosensor. Free Radic Biol Med 53:2240–2249CrossRefGoogle Scholar
  15. 15.
    Liu Y, Wei H, Jiang X, Guo H, Liu X (2018) Synthesis of metal–organic frameworks derived nanocomposites for superoxide anion radical sensing and cell monitoring upon oxidative stress. J Electroanal Chem 820:51–59CrossRefGoogle Scholar
  16. 16.
    Wang MQ, Ye C, Bao SJ, Xu MW, Zhang Y, Wang L, Ma XQ, Guo J, Li CM (2017) Nanostructured cobalt phosphates as excellent biomimetic enzymes to sensitively detect superoxide anions released from living cells. Biosens Bioelectron 87:998–1004CrossRefGoogle Scholar
  17. 17.
    Liu X, Ran M, Liu G, Liu X, Xue Z, Lu X (2018) A sensitively non-enzymatic amperometric sensor and its application in living cell superoxide anion radical detection. Talanta 186:248–255CrossRefGoogle Scholar
  18. 18.
    Liu L, Zhao H, Shi L, Lan M, Zhang H, Yu C (2017) Enzyme- and metal-free electrochemical sensor for highly sensitive superoxide anion detection based on nitrogen doped hollow mesoporous carbon spheres. Electrochim Acta 227:69–76CrossRefGoogle Scholar
  19. 19.
    Wang Y, Wang M, Lei L, Chen Z, Liu Y, Bao S (2018) FePO4 embedded in nanofibers consisting of amorphous carbon and reduced graphene oxide as an enzyme mimetic for monitoring superoxide anions released by living cells. Microchim Acta 185:140–145CrossRefGoogle Scholar
  20. 20.
    Seenivasan R, Kumar SN, Kalpana B, Govindaswamy I, Kumar SS, Chandran K (2011) Electrochemical sensor for simultaneous measurement of nitrite and superoxide anion radical using superoxide dismutase-mimetic manganese(III) Tetrakis(1-methyl-4-pyridyl)Porphyrin on Polypyrrole matrix. Sens Lett 9:1682–1688CrossRefGoogle Scholar
  21. 21.
    Ding A, Liu F, Zheng J, Chen J, Li C, Wang B (2018) Synthesis of manganese oxide embedded carbon nanofibers as effective biomimetic enzymes for sensitive detection of superoxide anions released from living cells. Macromol Mater Eng 303:1800079CrossRefGoogle Scholar
  22. 22.
    Hu FX, Kang YJ, Du F, Zhu L, Xue YH, Chen T, Dai LM, Li CM (2015) Living cells directly growing on a DNA/Mn3(PO4)2 -immobilized and vertically aligned CNT Array as a free-standing hybrid film for highly sensitive in situ detection of released superoxide anions. Adv Funct Mater 25:5924–5932CrossRefGoogle Scholar
  23. 23.
    Ding A, Wang B, Ma X, Diao J, Zheng J, Chen J, Li C (2018) DNA-induced synthesis of biomimetic enzyme for sensitive detection of superoxide anions released from live cell. RSC Adv 8:12354–12359CrossRefGoogle Scholar
  24. 24.
    Ma X, Hu W, Guo C, Yu L, Gao L, Xie J, Li CM (2014) DNA-templated biomimetic enzyme sheets on carbon nanotubes to sensitively in situ detect superoxide anions released from cells. Adv Funct Mater 24:5897–5903CrossRefGoogle Scholar
  25. 25.
    Shen X, Wang Q, Liu Y, Xue W, Ma L, Feng S, Wan M, Wang F, Mao C (2016) Manganese phosphate self-assembled nanoparticle surface and its application for superoxide anion detection. Sci Rep 6:28989–28998CrossRefGoogle Scholar
  26. 26.
    Peng F, Xu T, Wu F, Ma C, Liu Y, Li J, Zhao B, Mao C (2017) Novel biomimetic enzyme for sensitive detection of superoxide anions. Talanta 174:82–91CrossRefGoogle Scholar
  27. 27.
    Halim J, Cook KM, Naguib M, Eklund P, Gogotsi Y, Rosen J, Barsoum MW (2016) X-ray photoelectron spectroscopy of select multi-layered transition metal carbides. Appl Surf Sci 362:406–417CrossRefGoogle Scholar
  28. 28.
    Zhu X, Liu B, Hou H, Huang Z, Zeinu KM, Huang L, Yuan X, Guo D, Hu J, Yang J (2017) Alkaline intercalation of Ti3C2 MXene for simultaneous electrochemical detection of Cd(II), Pb(II), Cu(II) and Hg(II). Electrochim Acta 248:46–57CrossRefGoogle Scholar
  29. 29.
    Satheeshkumar E, Makaryan T, Melikyan A, Minassian H, Gogotsi Y, Yoshimura M (2016) One-step solution processing of Ag, Au and Pd@MXene hybrids for SERS. Sci Rep 6(32049)Google Scholar
  30. 30.
    Wang MQ, Ye C, Bao SJ, Xu MW (2017) Controlled synthesis of Mn3(PO4)2 hollow spheres as biomimetic enzymes for selective detection of superoxide anions released by living cells. Microchim Acta 184:1177–1184CrossRefGoogle Scholar
  31. 31.
    Batchelor-McAuley C, Yang M, Hall EM, Compton RG (2015) Correction factors for the analysis of voltammetric peak currents measured using staircase voltammetry. J Electroanal Chem 758:1–6CrossRefGoogle Scholar
  32. 32.
    Cai X, Shi L, Sun W, Zhao H, Li H, He H, Lan M (2018) A facile way to fabricate manganese phosphate self-assembled carbon networks as efficient electrochemical catalysts for real-time monitoring of superoxide anions released from HepG2 cells. Biosens Bioelectron 102:171–178CrossRefGoogle Scholar
  33. 33.
    Dashtestani F, Ghourchian H, Eskandari K (2015) A superoxide dismutase mimic nanocomposite for amperometric sensing of superoxide anions. Microchim Acta 182:1045–1053CrossRefGoogle Scholar
  34. 34.
    Madhurantakam S, Selvaraj S, Nesakumar N (2014) Electrochemical enzymeless detection of superoxide employing naringin–copper decorated electrodes. Biosens Bioelectron 59:134–139CrossRefGoogle Scholar
  35. 35.
    Santhosh P, Manesh KM, Lee SH (2011) Sensitive electrochemical detection of superoxide anion using gold nanoparticles distributed poly(methyl methacrylate)–polyaniline core–shell electrospun composite electrode. Analyst 136:1557–1561CrossRefGoogle Scholar
  36. 36.
    Chen XJ, West AC, Cropek DM, Banta S (2008) Detection of the superoxide radical anion using various Alkanethiol monolayers and immobilized cytochrome c. Anal Chem 80:9622–9629CrossRefGoogle Scholar
  37. 37.
    Sadeghian RB, Ostrovidov S, Han J, Salehi S, Bahraminejad B, Bae H, Chen M, Khademhosseini A (2016) Online monitoring of superoxide anions released from skeletal muscle cells using an electrochemical biosensor based on thick-film Nanoporous gold. ACS sensors 1:921–928CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Luminescent and Real-Time Analytical Chemistry, Ministry of Education, Faculty of Materials and EnergySouthwest UniversityChongqingPeople’s Republic of China
  2. 2.School of Chemistry and Chemical EngineeringAnkang UniversityAnkangPeople’s Republic of China

Personalised recommendations